CN118027367A - Method for manufacturing polyester for preservative film - Google Patents
Method for manufacturing polyester for preservative film Download PDFInfo
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- CN118027367A CN118027367A CN202211575477.3A CN202211575477A CN118027367A CN 118027367 A CN118027367 A CN 118027367A CN 202211575477 A CN202211575477 A CN 202211575477A CN 118027367 A CN118027367 A CN 118027367A
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- carboxylic acid
- acid
- aromatic carboxylic
- producing
- aliphatic
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- 239000003755 preservative agent Substances 0.000 title claims abstract description 25
- 230000002335 preservative effect Effects 0.000 title claims abstract description 25
- 229920000728 polyester Polymers 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 15
- -1 polybutylene adipate terephthalate Polymers 0.000 claims abstract description 37
- 239000004629 polybutylene adipate terephthalate Substances 0.000 claims abstract description 33
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 32
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 30
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920001896 polybutyrate Polymers 0.000 description 6
- 238000013461 design Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 210000003739 neck Anatomy 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 229960002479 isosorbide Drugs 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229960002920 sorbitol Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- JXIBVDIZHKJNKS-UHFFFAOYSA-N C(C)O[Ti+2]OCC Chemical compound C(C)O[Ti+2]OCC JXIBVDIZHKJNKS-UHFFFAOYSA-N 0.000 description 1
- YZVQYWUAHWFCFI-UHFFFAOYSA-N CC(C)(C)O[Ti](C(C)(C)C)(OC(C)(C)C)OC(C)(C)C Chemical compound CC(C)(C)O[Ti](C(C)(C)C)(OC(C)(C)C)OC(C)(C)C YZVQYWUAHWFCFI-UHFFFAOYSA-N 0.000 description 1
- CXRVNRVRMMXKKA-UHFFFAOYSA-N CC(C)O[Ti+2]OC(C)C Chemical compound CC(C)O[Ti+2]OC(C)C CXRVNRVRMMXKKA-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YFESLUXJCTZZFA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1.OCC1CCC(CO)CC1 YFESLUXJCTZZFA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- OVYQSRKFHNKIBM-UHFFFAOYSA-N butanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O OVYQSRKFHNKIBM-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- GJBRTCPWCKRSTQ-UHFFFAOYSA-N decanedioic acid Chemical compound OC(=O)CCCCCCCCC(O)=O.OC(=O)CCCCCCCCC(O)=O GJBRTCPWCKRSTQ-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XEUHNWODXVYLFD-UHFFFAOYSA-N heptanedioic acid Chemical compound OC(=O)CCCCCC(O)=O.OC(=O)CCCCCC(O)=O XEUHNWODXVYLFD-UHFFFAOYSA-N 0.000 description 1
- YVSCCMNRWFOKDU-UHFFFAOYSA-N hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)CCCCC(O)=O YVSCCMNRWFOKDU-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- YQXQWFASZYSARF-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC YQXQWFASZYSARF-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WPBWJEYRHXACLR-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O.OC(=O)CCCCCCCC(O)=O WPBWJEYRHXACLR-UHFFFAOYSA-N 0.000 description 1
- TWHMVKPVFOOAMY-UHFFFAOYSA-N octanedioic acid Chemical compound OC(=O)CCCCCCC(O)=O.OC(=O)CCCCCCC(O)=O TWHMVKPVFOOAMY-UHFFFAOYSA-N 0.000 description 1
- YKEKYBOBVREARV-UHFFFAOYSA-N pentanedioic acid Chemical compound OC(=O)CCCC(O)=O.OC(=O)CCCC(O)=O YKEKYBOBVREARV-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Polyesters Or Polycarbonates (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
Abstract
The invention provides a method for manufacturing polyester for a preservative film, which at least comprises the following steps. An aromatic carboxylic acid, an aliphatic carboxylic acid, and an aliphatic alcohol are provided, wherein the aromatic carboxylic acid includes at least two of phthalic acid, isophthalic acid, and terephthalic acid. The aromatic carboxylic acid, the aliphatic carboxylic acid and the aliphatic alcohol are subjected to at least esterification reaction, prepolymerization reaction and polymerization reaction in sequence to obtain the polybutylene adipate terephthalate.
Description
Technical Field
The invention relates to a method for manufacturing polyester for a preservative film.
Background
In general, materials used for the preservative film in the past are biodegradable materials (polyvinyl chloride (Polyvinylchloride) materials or Polyethylene (PE) materials), and as environmental awareness of the public increases, the public starts to choose environment-friendly biodegradable materials, such as polybutylene adipate terephthalate (Polybutylene ADIPATE TEREPHTHALATE, PBAT), to replace the biodegradable materials. However, polybutylene adipate terephthalate has poor physical properties (ductility, flexibility, resilience, etc.), and therefore, its applicability to use in preservative films and the like is limited.
Disclosure of Invention
The invention provides a method for manufacturing polyester for a preservative film, which can improve the physical property performance of polybutylene adipate terephthalate and further improve the applicability of the polybutylene adipate terephthalate to the preservative film.
The invention relates to a method for manufacturing polyester for a preservative film, which at least comprises the following steps. An aromatic carboxylic acid, an aliphatic carboxylic acid, and an aliphatic alcohol are provided, wherein the aromatic carboxylic acid includes at least two of phthalic acid, isophthalic acid, and terephthalic acid. The aromatic carboxylic acid, the aliphatic carboxylic acid and the aliphatic alcohol are subjected to at least esterification reaction, prepolymerization reaction and polymerization reaction in sequence to obtain the polybutylene adipate terephthalate.
In one embodiment of the present invention, the aliphatic carboxylic acid includes one or more of C4-C10 dicarboxylic acids.
In one embodiment of the present invention, the aliphatic alcohol includes one or more of C4-C12 diols.
In one embodiment of the present invention, in the above aromatic carboxylic acid, the total mole number of phthalic acid and isophthalic acid: the molar number of terephthalic acid ranges from 0.01:0.99 to 0.5:0.5.
In one embodiment of the present invention, in the above aromatic carboxylic acid, the mole number of phthalic acid: the molar number of isophthalic acid ranges from 0:1 to 1:0.
In one embodiment of the present invention, in the polybutylene adipate-terephthalate described above, the mole number of the aromatic carboxylic acid: the molar number of aliphatic carboxylic acid ranges from 0.55:0.45 to 0.2:0.8.
In one embodiment of the present invention, in the polybutylene adipate-terephthalate described above, the total mole number of the aromatic carboxylic acid and the aliphatic carboxylic acid: the molar number of aliphatic alcohol ranges from 45:55 to 55:45.
In an embodiment of the invention, the aromatic carboxylic acid and the aliphatic carboxylic acid have a total addition amount, and a ratio of the aliphatic carboxylic acid to the total addition amount ranges from 45mol% to 80 mol%.
In an embodiment of the invention, the polybutylene adipate terephthalate is applied to a preservative film.
In an embodiment of the invention, the proportion of the polybutylene adipate terephthalate in the preservative film is greater than 95wt%.
Based on the above, the present invention improves the production process of polyester, uses phthalic acid and/or isophthalic acid to partially replace terephthalic acid by the design of the starting material, so that the obtained polybutylene adipate terephthalate molecule becomes curved, the alignment property is reduced, the crystallinity is destroyed, and the physical property performance (such as self-viscosity and/or resilience) of polybutylene adipate terephthalate can be improved, and the applicability of the polybutylene adipate terephthalate in preservative films is further improved.
In order to make the above features and advantages of the present invention more comprehensible, embodiments accompanied with figures are described in detail below.
Drawings
Fig. 1 is a flow chart of a method for manufacturing a polyester for a preservative film according to an embodiment of the invention.
Detailed Description
In the following detailed description, for purposes of explanation and not limitation, example embodiments disclosing specific details are set forth in order to provide a thorough understanding of the various principles of the present invention. However, it will be apparent to one having ordinary skill in the art having had the benefit of the present disclosure, that the present invention may be practiced in other embodiments that depart from the specific details disclosed herein. In addition, descriptions of well-known devices, methods and materials may be omitted so as to not obscure the description of the various principles of the present invention.
Ranges may be expressed herein as from "about" one particular value to "about" another particular value, as well as directly to one particular value and/or to another particular value. When the range is expressed, another embodiment includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are obviously related to the other endpoint or independent of the other endpoint.
Non-limiting terms (such as may, for example, or the like) are used herein in a non-essential or alternative manner, including, adding or otherwise.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Fig. 1 is a flow chart of a method for manufacturing a polyester for a preservative film according to an embodiment of the invention. Referring to fig. 1, in step S100, an aromatic carboxylic acid, an aliphatic carboxylic acid and an aliphatic alcohol are provided, wherein the aromatic carboxylic acid includes at least two of phthalic acid, isophthalic acid and terephthalic acid. Then, in step S200, at least the aromatic carboxylic acid, the aliphatic carboxylic acid and the aliphatic alcohol are sequentially subjected to an esterification reaction, a prepolymerization reaction and a polymerization reaction to obtain polybutylene adipate terephthalate. Accordingly, the present embodiment improves the manufacturing method of polyester, uses phthalic acid and/or isophthalic acid to partially replace terephthalic acid by the design of the starting material, so that the obtained polybutylene adipate-terephthalate molecule becomes curved, the alignment property is reduced, the crystallinity is destroyed, and the physical property performance (such as self-viscosity and/or resilience) of polybutylene adipate-terephthalate can be improved, thereby improving the applicability of the polybutylene adipate-terephthalate in preservative films.
In some embodiments, the polybutylene adipate terephthalate is applied to the preservative film, and the polybutylene adipate terephthalate is, for example, more than 95wt% of the preservative film, and since the polybutylene adipate terephthalate prepared by the method for manufacturing the polyester of the embodiment has improved physical properties, it is not necessary to blend with other biodegradable polymers or fillers in order to meet the requirements of the preservative film, wherein the blending additive is, for example, acrylic ester which can be used for improving ductility and/or glycerin which can improve softness and adhesiveness, but the invention is not limited thereto.
In some embodiments, in the aromatic carboxylic acid, the total moles of phthalic acid and isophthalic acid: the molar number of terephthalic acid ranges from 0.01:0.99 to 0.5:0.5 (e.g., any ratio between 0.01:0.99, 0.05:0.95, 0.1:0.9, 0.2:0.8, 0.3:0.7, 0.4:0.6, 0.5:0.5, or 0.01:0.99 to 0.5:0.5), and the molar number of phthalic acid: the molar ratio of isophthalic acid ranges from 0:1 to 1:0 (e.g., any ratio of 0:1, 0.1:0.9, 0.3:0.7, 0.5:0.5, 0.7:0.3, 0.9:0.1, 1:0, or 0:1 to 1:0) (i.e., phthalic acid and isophthalic acid may be added alternatively or together), but the invention is not limited thereto, and the ratio of phthalic acid, isophthalic acid, terephthalic acid in aromatic carboxylic acid may be determined according to the actual design requirements, so long as the aromatic carboxylic acid includes at least two of phthalic acid, isophthalic acid, terephthalic acid, which are within the scope of the invention.
In some embodiments, the aliphatic carboxylic acid comprises one or more of a C4 to C10 dicarboxylic acid, for example, but the invention is not limited to, one or more of adipic acid (ADIPIC ACID), succinic acid (Succinic acid), glutaric acid (Glutaric acid), pimelic acid (PIMELIC ACID), suberic acid (Suberic acid), azelaic acid (Azelaic acid), sebacic acid (Sebacic acid).
In some embodiments, the molar number of aromatic carboxylic acid in the polybutylene adipate-terephthalate: the molar number of the aliphatic carboxylic acid ranges from 0.55:0.45 to 0.2:0.8 (for example, any one of the ratios between 055:45, 0.5:0.5, 0.4:0.6, 0.3:0.7, 0.2:0.8 or 0.55:0.45 to 0.2:0.8), but the present invention is not limited thereto.
In some embodiments, the softness and self-tackiness (the ability of the material to conform to the surface of an article) of polybutylene adipate-terephthalate may be further improved when the proportion of aliphatic carboxylic acid is increased, so that the proportion of aliphatic carboxylic acid added ranges from 45mol% to 80mol% (e.g., 45mol%, 55mol%, 65mol%, 75mol%, 80mol%, or any molar proportion between 45mol% and 80 mol%) based on the total amount of aromatic carboxylic acid and the aliphatic carboxylic acid added, but the invention is not limited thereto.
In some embodiments, the aliphatic alcohol comprises one or more of a C4-C12 diol (containing a straight or branched chain), for example, one or more of 1, 4-butanediol (14-BG), 1,4-cyclohexanedimethanol (1, 4-Cyclohexanedimethanol), isosorbide (isosorbide), 2,4:3, 5-bis-oxy-methylene-D-glucitol (2, 4:3, 5-Di-O-methylene-D-glucitol), but the invention is not so limited.
In some embodiments, in polybutylene adipate terephthalate, the total moles of aromatic carboxylic acid and aliphatic carboxylic acid: the molar number of the aliphatic alcohol ranges from 45:55 to 55:45 (for example, 45:55, 50:50, 55:45 or any ratio between 45:55 and 55:45), but the present invention is not limited thereto.
In some embodiments, when the long-chain aliphatic diol of C6-C12 is added, the softness and self-viscosity of the polybutylene adipate terephthalate can be further improved, for example, the ratio of the long-chain aliphatic diol of C6-C12 to the total addition amount of the aliphatic alcohol is between 0mol% and 50mol% (such as any mole ratio between 5mol%, 10mol%, 20mol%, 30mol%, 40mol% or 0mol% and 50 mol%), but the invention is not limited thereto.
The various reaction details in step S200 of fig. 1 are described further below as being optionally reacted with other materials. It should be noted that, a person having ordinary skill in the art can adjust parameters, order and process of the following steps according to actual needs, and the following steps are merely examples, and are not meant to limit the present invention.
< Esterification reaction >
In some embodiments, the reaction temperature of the esterification reaction is, for example, between 160 ℃ and 220 ℃, and the pressure is, for example, atmospheric pressure (about 760 torr), for example, the esterification reaction may be performed as follows. Step 1, using a 2L reaction flask (four necks), the uppermost neck was inserted with mechanical stirring, and the other three necks were: nitrogen inlet, thermocouple insertion port for temperature control, dean-stark device. And 2, sequentially weighing the aromatic carboxylic acid, the aliphatic carboxylic acid and the aliphatic alcohol, and adding the aromatic carboxylic acid, the aliphatic carboxylic acid and the aliphatic alcohol into a reaction bottle. And 3, placing the reaction bottle in a heating bag, setting the nitrogen flow to 40ml/min, setting the temperature to 190 ℃, starting a stirrer when the temperature is raised to 100 ℃, setting the rotating speed to 100rpm, setting the rotating speed of the stirrer to 200rpm when the temperature is raised to 140 ℃, measuring the acid value when the temperature is raised to 190 ℃, calculating the esterification rate, and confirming that the esterification rate is more than 70%. And step 4, raising the temperature to 220 ℃, continuously reacting for 1.5 hours, sampling and measuring the acid value, calculating the esterification rate, and confirming that the esterification rate is more than 90 percent.
< Prepolymerization reaction >
In some embodiments, the reaction temperature of the prepolymerization is, for example, between 160 ℃ and 220 ℃ and the pressure is, for example, less than 100 torr, for example, the prepolymerization can be performed as follows. Step 1, controlling the temperature to 180 ℃, and weighing Titanium catalyst (such as Titanium (IV) butoxide, titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) propoxide), titanium (IV) isopropoxide isopropoxide, titanium (IV) ethoxide ethoxide, tert-butyl Titanium (IV) tert-butoxide and 2-ethylhexanol Titanium (IV) 2-ethylhexyloxide) for adding the catalyst. And 2, vacuumizing to less than 100 Torr by using a vacuum pump, and after the pressure is stable, raising the temperature to 190 ℃ and reacting for 1 hour. And 3, the substances to be steamed are not steamed out, the temperature is increased to 220 ℃ and/or 230 ℃ and the reaction is carried out for 30 minutes. And 4, cooling to 200 ℃, closing a vacuum pump to break vacuum by nitrogen, discharging the stirring and temperature control device, and pouring out the PBAT prepolymer for cooling for standby.
< Polymerization reaction >
In some embodiments, the polymerization reaction temperature is, for example, between 230 ℃ and 250 ℃ and the pressure is, for example, less than 1 torr, for example, the polymerization reaction may be performed as follows. Step 1, the PBAT prepolymer obtained in the prepolymerization reaction was placed in a 2L polymerization reaction tank. And 2, closing a feeding hole after feeding is completed, and opening nitrogen to replace air in the tank (10 minutes). And 3, setting the temperature to 200 ℃, and gradually adjusting the rotating speed to 60rpm. And step 4, when the temperature and the rotating speed reach target values, starting a vacuum pump switch, and reducing the pressure to be less than 1 Torr. And 5, when the vacuum value reaches the target, setting the temperature to 245-250 ℃, and observing the change of the reaction torque value. And 6, after the torque value reaches a preset target, turning off the vacuum pump, and introducing nitrogen to return the system to normal pressure. And 7, if no subsequent other reaction is carried out, opening a barrel bottom valve of the reaction tank for discharging, and obtaining the PBAT product. Here, the polymerization reaction may be optionally assisted by the addition of a suitable catalyst, but the present invention is not limited thereto.
In some embodiments, step 7 of the polymerization reaction described above may optionally be followed by a further chain extension reaction. Further, the reaction temperature of the chain extension reaction is, for example, between 150 ℃ and 200 ℃, and the pressure is, for example, normal pressure (about 760 torr), for example, the chain extension reaction can be performed as follows. The temperature of the reaction tank is reduced to 200 ℃, nitrogen is continuously introduced, the rotation speed of a stirring shaft is maintained at 60rpm, and a chain extender (such as isocyanate: hexamethylene diisocyanate (Hexamethylene diisocyanate), dicyclohexylmethane-4, 4 '-diisocyanate (4, 4' -Diisocyanato-methylenedicyclohexane) and/or ADR series: ADR4468, ADR4368 and ADR 4370) is added into the reaction tank, and after the reaction is carried out for 5 to 20 minutes, a barrel bottom valve of the reaction tank is opened for discharging, thus obtaining the PBAT product.
Table 1 below provides the composition of components specifically used in the above-described polyester production method of the present invention and the corresponding efficacy data (the numerical units of the raw materials shown in table 1 are weight ratios), so the polyester production method of the present invention can be surely implemented, however, these data are illustrative, the present invention is not limited to these examples, and comparative examples may be #1 and #4 (terephthalic acid only is used). Here, the self-adhesion (adhesive force) test in table 1 is performed by cutting a preservative film (thickness may be 7 to 15 micrometers (μm)) made of a corresponding PBAT raw material into 3cm x10cm, taking two preservative films and bonding the two preservative films with 1Kg roller (normal temperature), and then analyzing the peel strength of the materials with a tensile tester, wherein the higher the value is, the better the self-adhesion is, and the better the adhesion between the films is; the elastic force was evaluated by using a rotary rheometer, wherein the tensile test was performed by using the rotary rheometer, the test piece was 1cm (width) and 10cm (length), the tensile test piece was stretched to 10% deformation (for example, 10cm was stretched to 11 cm) by using the rotary rheometer (25 ℃ C.), the force (F1) required for maintaining the deformation was measured, the deformation was maintained until 120 seconds, the force (F2) required for maintaining the deformation was obtained, and F2/F1 was 100% of the elastic force as defined. It should be noted that when the elastic force is high, it represents that the elastic force is easy to rebound when stretched, and thus the problem of being difficult to be attached to an article is caused.
TABLE 1
In summary, the present invention improves the production process of polyester, uses phthalic acid and/or isophthalic acid to partially replace terephthalic acid by the design of the starting material, so that the obtained polybutylene adipate terephthalate molecule becomes curved, reduces the alignment property and damages the crystallinity, thereby improving the physical property performance (such as self-adhesion and/or resilience) of polybutylene adipate terephthalate, and further improving the applicability of the polybutylene adipate terephthalate in preservative films.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A method for producing a polyester for a preservative film, comprising:
providing an aromatic carboxylic acid, an aliphatic carboxylic acid, and an aliphatic alcohol, wherein the aromatic carboxylic acid comprises at least two of phthalic acid, isophthalic acid, terephthalic acid; and
The aromatic carboxylic acid, the aliphatic carboxylic acid and the aliphatic alcohol are subjected to at least esterification reaction, prepolymerization reaction and polymerization reaction in sequence to obtain the polybutylene adipate terephthalate.
2. The method of producing a polyester according to claim 1, wherein the aliphatic carboxylic acid comprises one or more of C4 to C10 dicarboxylic acids.
3. The method of producing a polyester according to claim 1, wherein the aliphatic alcohol comprises one or more of C4 to C12 diols.
4. The method for producing a polyester according to claim 1, wherein in the aromatic carboxylic acid, the total mole number of the phthalic acid and the isophthalic acid is: the molar number of terephthalic acid ranges from 0.01:0.99 to 0.5:0.5.
5. The method for producing a polyester according to claim 1, wherein in the aromatic carboxylic acid, the mole number of phthalic acid: the molar number of isophthalic acid ranges from 0:1 to 1:0.
6. The method for producing a polyester according to claim 1, wherein in the polybutylene adipate terephthalate, the molar number of the aromatic carboxylic acid is: the molar number of the aliphatic carboxylic acid ranges from 0.55:0.45 to 0.2:0.8.
7. The method for producing a polyester according to claim 1, wherein in the polybutylene adipate-terephthalate, the total mole number of the aromatic carboxylic acid and the aliphatic carboxylic acid is as follows: the molar number of the aliphatic alcohol ranges from 45:55 to 55:45.
8. The method for producing a polyester according to claim 1, wherein the aromatic carboxylic acid and the aliphatic carboxylic acid have a total addition amount, and the ratio of the aliphatic carboxylic acid addition amount to the total addition amount is in a range of 45mol% to 80 mol%.
9. The method of producing a polyester according to claim 1, wherein the polybutylene adipate terephthalate is used for a preservative film.
10. The method of producing a polyester according to claim 9, wherein the polybutylene adipate terephthalate is more than 95wt% of the preservative film.
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| Application Number | Priority Date | Filing Date | Title |
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| TW111143216A TWI815727B (en) | 2022-11-11 | 2022-11-11 | Manufacturing method of polyester for plastic wrap |
| TW111143216 | 2022-11-11 |
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| CN118027367A true CN118027367A (en) | 2024-05-14 |
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| CN202211575477.3A Pending CN118027367A (en) | 2022-11-11 | 2022-12-08 | Method for manufacturing polyester for preservative film |
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| US (1) | US20240158570A1 (en) |
| JP (1) | JP2024070776A (en) |
| CN (1) | CN118027367A (en) |
| TW (1) | TWI815727B (en) |
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- 2022-11-11 TW TW111143216A patent/TWI815727B/en active
- 2022-12-08 CN CN202211575477.3A patent/CN118027367A/en active Pending
- 2022-12-15 US US18/081,708 patent/US20240158570A1/en active Pending
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| TWI815727B (en) | 2023-09-11 |
| JP2024070776A (en) | 2024-05-23 |
| US20240158570A1 (en) | 2024-05-16 |
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